DETERGENT COMPOSITION FOR HARD SURFACE

Abstract: A detergent composition for hard surfaces is disclosed, which contains: (a) a mixture consisting of at least two compounds represented by formula (I), wherein s is an integer from 1 to 10, representing the number of moles of the ethylene oxide group, which are different in degree of polymerization, said mixture (a) satisfying relationship (1), wherein Nt is the percent by weight of a compound having t mol of the oxyethylene group added based on the weight of mixture (a). The detergent composition has excellent detergency and foaming properties and is useful for removal of denatured oily dirt in the kitchen.

Description: DETERGENT COMPOSITION FOR HARD SURFACE FIELD OF THE INVENTION This invention relates to a detergent composition for a hard surface and more particularly a detergent composi¬ tion having excellent foaming properties which effective¬ ly, safely and rapidly removes clinging dirt, such as greasy dirt on tiles, enameled ironware, etc. in a kitchen that is the cooking oil splashed during cooking and dena¬ tured with heat or time. BACKGROUND OF THE INVENTION A ventilator, a stove, etc. in the kitchen of homes easily get greasy with an oily and sticky substance that, is difficult to remove. This oily dirt is denatured cooking oil which has splashed or smoked during deep- frying or shallow-frying and stuck to the surface of the ventilator, the stove, etc. In general, many kinds of cooking oil have a chemical structure containing an unsat- urated double bond. Such oil easily undergoes oxidation or polymerization on exposure to air for a long time under action of heat or light to gradually increase its molecu¬ lar weight into resinous- matter. This is the substance of the denatured oily dirt which is the cause of difficulty in cleaning the kitchen. The ventilator in homes, if left uncleaned, gets stained with a notable amount of oily dirt and becomes unsightly in about 6 months. By that time, the adhered oil has undergone considerable denaturation with strong adhesion to the substrate, turning into heavy dirt that cannot be easily removed. Detergent compositions contain¬ ing an alkylene glycol ether type solvent, such as butyl carbitol, have been used for removal of such dirt. Howev¬ er, these detergent compositions were unsatisfactory for their ill smell and insufficient detergent action. In order to solve the above-described problems, Japanese Patent Application Public Disclosure No. 10808/76 proposes to use hexylene glycol in combination with an alkylene glycol ether solvent to provide a safe detergent composition which has enhanced detergency and is substan¬ tially odorless. Further, Japanese Patent Application Public Disclo¬ sure No. 236300/89 discloses a detergent for hard surfaces which contains a polyoxyalkylene monobenzyl ether with the number of moles of the polyoxyalkylene added being not more than 5. According to the description of the publica¬ tion, this detergent lathers nicely. However, these conventional detergents are still unsatisfactory in detergency for heavy oily dirt, particu¬ larly those denatured under influences of temperature, humidity, and oxygen. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a detergent composition for hard surfaces (herein¬ after simply referred to as hard surface detergent compo¬ sition) which is excellent in swelling properties and detergency for heavy dirt, such as oil denatured under influences of temperature, humidity, oxygen, etc., and is capable of rapid cleansing. As a result of extensive investigations, the present inventors have found that the above object of the present invention is accomplished by a detergent composition containing a mixture consisting of at least two polyox- yethylene monophenyl ethers different in degree of poly¬ merization at a specific mixing ratio. The present inven¬ tion has been completed based on this finding. The present invention provides a hard surface deter¬ gent composition containing (a) a mixture consisting of at least two compounds represented by formula (I): / Q- 0 - (CH 2 CH 2 0) S H (I) wherein s is an integer of from 1 to 10, representing the number of moles of the ethylene oxide group, which are different in degree of polymerization, the mixture satis¬ fying relationship (1): 99/1 ≥ ,≥ 15/85 (1) whereinNt is the percent by weight of a compound having tmol of the oxyethylene group added based on the weight of mixture (a) . DETAILED DESCRIPTION OF THE INVENTION The hard surface detergent composition of thepresent invention will be illustrated below in greater detail. Thecompounds represented by formula (I) which constitute component (a) are polyoxyethylenemonophenyl ethers. Component (a) is a mixture of at least two polyoxyethylene monophenyl ethers different in degree of polymerization. Fromthe stand- pointof swelling or dissolving action on oily dirt, particularly denaturedoily dirt, component (a) should satisfy relationship (1) , preferably relationship (2) , still preferably relationship (3) , yet preferably relationship (4) , andmost preferably rela¬ tionship (5) : 99 ,≥ 15/85 (1) whereinNt is the percent by weight of a compound having tmol of the oxyethylene group added based on the weight of mixture (a) (hereinafter the same) . 99/1 ≥ j " N,/ | |N,.≥ 15/85 ••• (2) 8/2 ≥ [][ Nt/ UN.≥ 15/85 (3) 5/5≥ ,'_. N t / t '. 4 6 N,≥35/ 65 (4) Further, it is preferable that component (a) satisfy¬ ing relationship (2), (3), (4) or (5) satisfies relation¬ ship (6): The process for preparing component (a) is not par¬ ticularly limited. For example, component (a) can be obtained by a process comprising arbitrarily selecting at least one compound of formula (I) in which s is between 1 and 3 and at least one compound of formula (I) in which s is between 4 and 10, preferably between 4 and 6, and mixing them together at such a ratio that satisfies any of relationships (1) to (5), or a process comprising reacting phenol with ethylene oxide in the presence of an alkali catalyst, such as sodium hydroxide or potassium hydroxide. Component (a) is a mixture of at least two of the above-mentioned polyoxyethylene monophenyl ethers, the two having different degrees of polymerization. While a single compound of formula (I) in which s is from 1 to 3 or from 4 to 10 is expected to exhibit detergent effects on oily dirt or slightly denatured oily dirt, the action of swelling and dissolving denatured oil can be accelerat¬ ed by mixing a compound in which s is from 1 to 3 and a compound in which s is from 4 to 10, preferably from 4 to 6, at a specific ratio satisfying any of the relationships (1) to (5). It is preferable that the detergent composition of the present invention further contains (b) an alkali agent (hereinafter referred to as component (b)). While not limiting, the alkali agent as component (b) preferably includes ammonia and alkanolamines. In partic¬ ular, monoethanolamine and diethanolamine are preferred for their hydrolytic action on denatured oil, leading enhanced detergency. These alkali agents may be used either individually or in combination of two or more thereof. Components (a) and (b) are preferably used at a weight ratio of 1/10 (b)/(a) _<_ 10/1, particularly 1/10 < , (b)/(a) <_ 1/1. If the ratio (b)/(a) is less than 1/10, the effect of addition of component (b) is insubstantial. A (b)/(a) ratio greater than 10/1 is uneconomical; for detergency reaches saturation. If is also preferable that the detergent composition furthermore contains (c) a surface active agent (hereinaf¬ ter referred to as component (c)). Component (c) imparts satisfactory detergency and foaming properties to the detergent composition. In particular, when the detergent composition is applied by spraying or with a squeeze foamer, component (c) markedly improves retention of the composition, thereby synergistically increasing the swell¬ ing action of component (a) on denatured oily dirt. While not limiting, component (c) preferably includes the following nonionic, amphoteric or anionic surface active agents. From the viewpoint of detergency, foaming properties, and low irritation, suitable nonionic surface active agents include polyoxyethylene alkyl ethers, polyoxyethyl¬ ene alkenyl ethers, higher fatty acid alkanolamides, polyoxyethylene higher fatty acid alkanolamides, amine oxides, and alkyl glycosides, with alkyl glycosides being especially preferred. Specific examples of the nonionic surface active agents are polyoxyethylene(p=3) lauryl ether, polyoxyethylene (p=7) lauryl ether, polyoxyethyl- ene(p=12) lauryl ether, dodecyl maltoside, coconut oil fatty acid diethanolamide, polyoxyethylene(p=2) coconut oil fatty acid monoethanolamide, and lauryldimethylamine oxide (p represents an average degree of polymerization). These nonionic surface active agents may be used either individually or in combination of two or more thereof. From the standpoint of detergency and foaming proper¬ ties, suitable amphoteric surface active agents include alkylamidocarbobetaines and alkylamidosulfobetaines. Specific examples are lauramidopropyl-N,N-dimethyl-acetic acid betaine, myristamidopropyl-N,N-dimethyl-acetic acid betaine, and cocoamidopropyl-N,N-dimethyl-acetic acid be¬ taine. These amphoteric surface active agents may be used either individually or in combination of two or more thereof. Suitable anionic surface active agents include alkyl- benzenesulfonates, alkylene oxide-added alkyl or alkenyl ether sulfates, olefinsulfonates, alkanesulfonates, satu¬ rated or unsaturated fatty acid salts, alkylene oxide- added alkyl or alkenyl ether carboxylates, and α - sulfofatty acid salts or esters. The counter ions forming these salts include alkali metal ions, e.g., a sodium ion and a potassium ion, an ammonium ion, and alkanolammonium ions, e.g., a monoethanolammonium ion, a diethanolammonium ion and a triethanolammonium ion. • The anionic surface active agents may be used either individually or in combi- nation of two or more thereof. The nonionic, amphoteric and anionic surface active agents may be used either individually or in combination thereof. Of the above-enumerated surface active agents as component (c), preferred are nonionic surface active agents or amphoteric surface active agents, and particu¬ larly nonionic surface active agents, with alkyl glyco¬ sides being most preferred, for their detergency for denatured oily dirt. The alkyl glycosides which can be used as component (c) preferably include those represented by formula (II): R 2 (OR 3 ) χ G (II) wherein R 2 represents an alkyl group, an alkenyl group or an alkylphenyl group each having from 8 to 18 carbon atoms, the alkyl moiety of which may be straight or branched; R3 represents an alkylene group having from 2 to 4 carbon atoms; G represents a residue of a reducing sugar having from 5 to 7 carbon atoms, such as glucose; x repre¬ sents a number of from 0 to 5 in average; and y represents a number of from 1 to 10 in average. Water solubility and crystallinity of the alkyl glycoside can be adjusted by varying x in formula (II) between 0 and 5 in average. x is preferably from 0 to 2, still preferably 0. Where y in formula (II) is greater than 1 in average, the sugar chains may be bonded through a 1-2 bond, a 1-3 bond, a 1-4 bond or a 1-6 bond or an a - or β -pyranoside or furanoside linkage or a mixture there¬ of, y is preferably from 1 to 10, still preferably from 1 to 1.5, yet preferably from 1.1 to 1.4. y can be measured by proton NMR. R 2 in formula (II) is preferably an alkyl group having from 10 to 14 carbon atoms from the standpoint of solubility and detergency. R3 is preferably an alkylene group having 2 or 3 carbon atoms from the standpoint of water solubility. The structure of G is decided by the starting mono-, di- or polysaccharide. The starting material for G preferably includes glucose and fructose as a monosaccharide and maltose and sucrose as a di- or polysaccharide from the standpoint of availability and cost. Glucose is particularly preferred for its avail¬ ability. Where an alkyl glycoside (hereinafter referred to as component (c-D) is used, it is recommended to use it in combination with an amphoteric surface active agent (hereinafter referred to as component (c-2)), preferably an alkylamidocarbobetaine, for improving the quality of lather, such as foaming properties and foam stability. In this case, components (c-1) and (c-2) are preferably used at a (c-l)/(c-2) weight ratio of 1/10 or higher for deter- gency and not higher than 10/1 for foaming properties, still preferably from 1/8 to 8/1, and yet preferably from 1/5 to 5/1. It is preferable that components (c) and (b) are used at a (c)/(b) weight ratio of from 1/10 to 10/1, particu¬ larly from 1/10 to 1/1. If that ratio is smaller than 1/10, the effect of improving detergency is insubstantial. The (c)/(b) ratio exceeding 10/1 is uneconomical. The hard surface detergent composition according to the present invention is prepared in a usual manner by mixing the essential component (a) , preferably components (a) and (b), still preferably components (a), (b) , and (c-1), yet preferably components (a), (b) , (c-1), and (c- 2), with water (hereinafter referred to as component (d) ) , if desired together with other optional components herein¬ after described, to obtain an aqueous solution. Component (a) is used in a proportion of from 0.1 to 30 parts by weight, preferably from 1 to 20 parts by weight, still preferably from 3 to 15 parts by weight, per 100 parts by weight of the total weight of components (a) to (d) . If the proportion of component (a) is less than 0.1 part, sufficient detergency cannot be obtained. A proportion of higher than 30 parts, at which the effects reach saturation, is uneconomical. Component (b) is used at a proportion of from 0.01 to 20 parts by weight, preferably from 0.05 to 10 parts by weight, per 100 parts by weight of the total weight of components (a) to (d). If the proportion of component (b) is less than 0.01 part, the detergency tends to be insuf¬ ficient. A proportion of higher than 20 parts, at which the effects reach saturation, is uneconomical. Component (c) is used in a proportion of from 0.1 to 20 parts by weight, preferably from 0.1 to 15 parts by weight, more preferably from 1 to 10 parts by weight, per 100 parts by weight of the total weight of components (a) to (d). If the proportion of component (c) is less than 0.1 part, the detergency tends to be insuff cient. A proportion higher than 20 parts, at which the effects reach saturation, is uneconomical. Component (d) is preferably used at a proportion of from 30 to 99.5 parts by weight, still preferably from 75 to 95 parts by weight. If desired, the hard surface detergent composition of the present invention may contain other optional compo¬ nents, such as a sequestering agent, a low-temperature stabilizer, a viscosity modifier, and the like. Any of commonly employed sequestering agents may be used in the present invention without restriction. Suit¬ able sequestering agents include hydroxycarboxylic acids, e.g., citric acid and malic acid; condensed phosphoric acids, e.g., pyrophosphoric acid; aminocarboxylic acids, e.g., ethylenediaminetetraacetic acid and hydroxyethylene- diamineacetic acid; and alkali meal (Na or K) salts, ammonium salts or alkanolamine salts thereof and their water-soluble salts. These sequestering agents may be used either individually or in combination of two or more thereof. The sequestering agent is used in an amount of from 0.001 to 20 parts by weight per 100 parts by weight of the total weight of components (a) to (d). Useful low-temperature stabilizers include lower alcohols, e.g., ethyl alcohol; lower glycols, e.g., ethyl¬ ene glycol; and lower alkylbenzenesulfonates, e.g., ben- zenesulfonates and toluenesulfonates. The low-temperature stabilizer is usually used in an amount of from 0.1 to 20 parts by weight per 100 parts by weight of the total weight of components (a) to (d). Useful viscosity modifiers include smectites, acrylic homo- or copolymers, such as sodium polyacrylate, cross- linked polyacrylic acids, and polyalkyl acrylates, polyvi- nyl alcohol, hydroxyethyl cellulose, carboxymethyl cellu¬ lose, polyvinyl pyrrolidone, and maleic anhydride poly¬ mers. The viscosity modifier is used in an amount of from 0.1 to 10 parts by weight per 100 parts by weight of the total weight of components (a) to (d). In order to enhance the commercial value of the detergent composition, the composition may further contain perfumes, colorants, antiseptics, antioxidants, thicken¬ ers, and so on. The hard surface detergent composition according to the present invention can be used, for example, by bring¬ ing dirt into contact with the composition for 5 to 30 minutes by, for example, soaking and removing the thus released and floated dirt. The contact time may be ex¬ tended to 5 to 10 hours for heavy dirt. Where the compo¬ sition is applied to a slanted or vertical surface, the detergent composition may be foamed and sprayed thereto to assure retention on the surface. The present invention will now be illustrated in greater detail with reference to Examples in view of Comparative Examples, but it should be understood that the present invention is not deemed to be limited thereto. EXAMPLES 1 AND COMPARATIVE EXAMPLES 1 TO 7 A detergent composition having the composition shown in Table 1 below (unit: wt%) was prepared and subjected to a swelling test in accordance with the following test meth¬ od. The results obtained are shown in Table 1. Swelling Test: Fourteen milligrams of rapeseed oil were baked on a Teflon-coated plate at 180 " C for 10 hours to prepare a denatured oil cake. The denatured oil cake was soaked in 2 ml of the detergent composition for 5 hours, and the swell (Q) of the cake was obtained as follows. D p w b Q = 1 + ( 1) D s w a wherein D_ is a density of a denatured oil; D_ • _> is a densi- ty of a detergent composition; W Q is a weight of a non- treated denatured oil; and W^ is a weight of a swollen denatured oil. TABLE 1 Example Comparative Example No. 1 1 2 3 4 5 6 (5)-0-(CH2CH 2 0)n7H *1 10 (θ)H } -(CH 2 CH 2 0) H n=l*2 10 (θ/H)-(CH2CH 2 0)-H n=2*3 10 (θ)-0-<CH 2 CH 2 0)-H n=3*4 10 (θ)H)-{CH 2 CH 2 0)-H n=4*5 10 (θ)-0-(CH2CH 2 0)-H n=5*6 10 (θ)-0-(CH 2 CH2θ)τ-H n=6*7 10 Butyl carbitol 10 Polyoxyethylene 2 (p*8=7) lauryl ether Monoethanolamine 5 5 5 5 5 5 5 Water bal.*9 bal. bal. bal. bal. bal. bal. bal. Swell (Q) 4.4 2.7 3.6 3.3 3.2 3.2 2.9 2.5 Note : *1: A mixture having the following ethylene oxide (EO) distribution: EO 1 mol=4 wt%; EO 2 mol=27 wt%; EO 3 mol=32 wt%; EO 4 mol=22 wt%; EO 5 mol=ll wt%; EO 6 mol=4 wt% *2: Commercially available reagent of first grade, produced by Kanto Chemical Co. , Ltd. *3: Hisolve DHP, produced by Toho Chemical Industry Co., Ltd. *4 and *5: Obtained by adding ethylene oxide to phenol and purified by distillation. *6: Synthesized by tosylating the hydroxyl group of the compound wherein n=2 and reacting it With HO-CH 2 CH 2 -0-CH 2 CH 2 -0-CH 2 CH 2 -OH by refluxing in dioxane in the presence of sodium hydroxide. *7: Synthesized by tosylating the hydroxyl group of the compound wherein n=2 and reacting it with HO-CH 2 CH 2 -0-CH 2 CH 2 -0-CH 2 CH 2 -0-CH 2 CH 2 -OH by refluxing in dioxane in the presence of sodium hydroxide. *8: Average degree of polymerization. *9: Balance EXAMPLES 2 TO 4 AND COMPARATIVE EXAMPLES 8 TO 9 A detergent composition having the composition shown in Table 2 below (unit: wt%) was prepared and subjected to a swelling test in the same manner as in Example 1. Fur¬ ther, the detergency and foaming properties of the compo¬ sition were evaluated according to the following test methods. The results obtained are shown in Table 2. Detergency Test: Frying oil was uniformly applied to an iron plate and baked at 180° C for 10 hours to prepare a plate with an almost dried film as a dirt model for a detergency test. The detergent composition was dropped on the vertically set plate with a dirt model and allowed to stand for 40 seconds. The released and floated dirt was lightly wiped off with absorbent wadding, and the degree of cleansing (detergency) was observed with the naked eye and rated according to the following standard. A ... The dirt was completely removed. B ... About 80% of the dirt was removed. C ... About 60% of the dirt was removed. D ... About 50% of the dirt was removed. E ... About 30% of the dirt was removed. F ... Dirt was not removed at all. Test of Foaming Properties: The detergent composition was sprayed onto a window- pane by means of a commercially available sprayer. The lather formed on spraying was visually observed and rated as follows. A ... Good lather. B ... Slight lather. C ... No lather. TABLE 2 Compara. Compara. Example Example Example Example Example Component (a) : Formula (I)*l: S*2 6.6 7.5 8.1 0.7 N*3 3.4 2.5 1.9 9.3 Component (b) : Monoethanolamine 5 Diethanolamine Component (c) : Polyoxyethylene lauryl ether (p*4=3) Dodecyl maltoside 3 Lauryldimethyl- 1 amine oxide Sodium lauryl- benzenesulfonate Sodium stearyl- sulfate Ethanol 10 Water bal.*5 bal. bal. bal. bal. Evaluation: Detergency B Foaming Pro- A A A C B perties Swell (Q) 4.8 4.5 4.1 2.0 3.0 Note: *1: A mixture having ethylene oxide distribution shown in Table 3. Σ t-3 *2: t-I N, *4: Average degree of polymerization. *5: Balance TABLE 3 Comparative Example No. Example No. θ}-0-(CH 2 CH 2 0)-H n=l (θ)-0- ( CH 2 CH 2 0)-H n=2 <2-0-<CH 2 CH 2 0)-H n=3 0.7 (5)-0- ( CH 2 CH 2 0)-H n= =4 2.25 <O>-0-CCH 2 CH 2 0).H n=5 (θ)-0-CGH 2 CH 2 0)-H n=6 0.85 It can be seen from the above results that the hard surface detergent composition of the present invention is excellent in swelling properties and detergency for oily dirt. In addition, the hard surface detergent composition was proved capable of rapid cleansing. As described and demonstrated above, the hard surface detergent composition comprising component (a) has excel¬ lent swelling properties and detergent action on dirt difficult to remove, such as oil having denatured under the influences of temperature, humidity, oxygen, etc. and is capable of rapid cleansing. In particular, the hard surface detergent composition comprising components (a) to (d) at a specific ratio shows further improvements. The hard surface detergent composition of the present invention is particularly useful for removing denatured oily dirt. While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims: CLAIM 1. A detergent composition for hard surfaces containing (a) a mixture consisting of at least two compounds repre¬ sented by formula (I): wherein s is an integer of from 1 to 10, representing the number of moles of the ethylene oxide group, which are different in degree of polymerization, said mixture (a) satisfying relationship (1): wherein N fc is the percent by weight of a compound having t mol of the oxyethylene group added based on the weight of mixture (a). 2. A detergent composition for hard surfaces as claimed in claim 1, wherein said composition further contains (b) an alkali agent. 3. A detergent composition for hard surfaces as claimed in claim 1, wherein said composition further contains (c) at least one surface active agent. 4. A detergent composition for hard surfaces containing (a) from 0.1 to 30 parts by weight of a mixture consisting of at least two compounds represented by formula (I) wherein s is an integer of from 1 to 10, representing the number of moles of the ethylene oxide group, which are different in degree of polymerization, said mixture (a) satisfying relationship (1): 99/1 ≥ ]_ " N,/ 15/85'" (1) whereinNt is the percent byweight of a compound having tmol of the oxyethylene group added based on the weight of mixture (a) , (b) from 0.01 to 20 parts byweight of an alkali agent, (c) from 0.1 to 20 parts by weight of at least one surface active agent, and (d) water, each per 100 parts by weight of the total weight of components (a) to (d) . 5. A detergent composition for hard surfaces as claimed in claim 4, wherein component (b) is ammonia or an alkanolamine. 6. A detergent composition for hard surfaces as claimed in claim 4, wherein component (c) is a nonionic surface active agent. 7. A detergent composition for hard surfaces as claimed in claim 6, wherein said nonionic surface active agent is an alkyl glycoside. 8. A detergent composition for hard surfaces as claimed in claim 4, wherein component (c) comprises (c-1) an alkyl glycoside and (c-2) an amphoteric surface active agent at a (c-l)/(c-2) weight ratio of from 1/10 to 10/1. 9. A detergent composition for hard surfaces as claimed in any of claims 4 to 8, wherein said detergent composi¬ tion is for removal of denatured oily dirt. 10. A method for removing denatured oily dirt on hard surfaces using a detergent composition for hard surfaces claimed in any of claims 4 to 8.

Inventors: JIN NORIKAZU, KUBOTA MASAKAZU, NAGUMO HIROSHI, TSUKUDA KAZUNORI, JIN, NORIKAZU, KUBOTA, MASAKAZU, NAGUMO, HIROSHI, TSUKUDA, KAZUNORI
Applicants: JIN NORIKAZU, KAO CORP, KUBOTA MASAKAZU, NAGUMO HIROSHI, TSUKUDA KAZUNORI, JIN, NORIKAZU, KAO CORPORATION, KUBOTA, MASAKAZU, NAGUMO, HIROSHI, TSUKUDA, KAZUNORI
Application year: 1994
Main classification: C11D3
IPC codes: C11D1, C11D3, C11D7